EP4074761A1 - Préimprégné, stratifié et article moulé intégré - Google Patents

Préimprégné, stratifié et article moulé intégré Download PDF

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Publication number
EP4074761A1
EP4074761A1 EP20897743.9A EP20897743A EP4074761A1 EP 4074761 A1 EP4074761 A1 EP 4074761A1 EP 20897743 A EP20897743 A EP 20897743A EP 4074761 A1 EP4074761 A1 EP 4074761A1
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EP
European Patent Office
Prior art keywords
resin
laminate
prepreg
epoxy
epoxy resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20897743.9A
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German (de)
English (en)
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EP4074761A4 (fr
Inventor
Jun Misumi
Masato Honma
Kyoko Shinohara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
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Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Publication of EP4074761A1 publication Critical patent/EP4074761A1/fr
Publication of EP4074761A4 publication Critical patent/EP4074761A4/fr
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
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    • B32B7/03—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers with respect to the orientation of features
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    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • B32B2250/02—2 layers
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Definitions

  • the present invention relates to a prepreg in which an epoxy resin and a thermoplastic resin are impregnated into a reinforcing fiber, and to a laminate or an integrated product containing the epoxy resin, the thermoplastic resin, and the reinforcing fiber.
  • a fiber-reinforced composite material that combines a thermosetting resin or a thermoplastic resin as a matrix with a reinforcing fiber such as a carbon fiber and a glass fiber is a lightweight material yet having excellent mechanical properties such as strength and rigidity, as well as excellent heat resistance and corrosion resistance. Therefore, this has been used in numerous fields, including aerospace, automobiles, railway vehicles, marine vessels, civil engineering and construction, and sporting goods.
  • these fiber-reinforced composite materials are not suitable for manufacturing of a part and a structural body having a complex shape in a single molding process. For the applications described above, it is necessary to prepare a member made of a fiber-reinforced composite material and then to integrate this with a similar or different type of a member.
  • a mechanical bonding method using a bolt, a rivet, a screw, or the like, and a bonding method using an adhesive are used to integrate a fiber-reinforced composite material composed of a reinforcing fiber and a thermosetting resin with a similar or a different member.
  • the mechanical bonding method requires a pre-processing process of a bonding portion, such as drilling of a hole, which leads to not only the increase in the time in the manufacturing process and in the manufacturing cost, but also the decrease in the material strength due to drilling of the hole.
  • the bonding method using an adhesive requires bonding and curing processes, which include preparation and application of the adhesive; thus, this leads to the increase in the time in the manufacturing process and to the insufficient reliability in terms of the adhesion strength.
  • a thermoplastic resin as the matrix bonds between members by welding in addition to the mechanical bonding method and the bonding method using an adhesive as described above; thus, it is possible to reduce the time necessary for bonding between members.
  • mechanical properties at a high temperature and an excellent resistance to chemicals are required as in the case of an aircraft structural member, there has been a problem in that the heat resistance and the chemical resistance thereof were not so good as those of the fiber-reinforced composite material composed of a thermosetting resin and a reinforcing fiber.
  • Patent Literature 1 describes a method for bonding a fiber-reinforced composite material composed of a thermosetting resin and a reinforcing fiber via an adhesive.
  • Patent Literature 2 describes a method for integrating a member formed of a thermoplastic resin with a member formed of a fiber-reinforced composite material that is obtained from a thermosetting resin. Specifically, a thermoplastic resin film is laminated to the surface of a prepreg sheet composed of a reinforcing fiber and the thermosetting resin, and then, this is heated and pressurized to obtain a fiber-reinforced composite material. The resulting fiber-reinforced composite material is then placed in a mold, and then, the thermoplastic resin is injection molded to bond the thermoplastic resin member formed by injection molding with the fiber-reinforced composite material.
  • Patent Literature 3 describes a method for manufacturing a laminate in which a thermoplastic resin adhesive layer is formed on the surface of a composite material composed of a thermosetting resin and a reinforcing fiber. It is described that this shows the adhesive effect with other members via a thermoplastic resin.
  • Patent Literature 4 describes a prepreg and its fiber-reinforced composite material, in which a particle, or a fiber, or a film formed of a thermoplastic resin is placed on the surface layer of a prepreg composed of a reinforcing fiber and a thermosetting resin.
  • Patent Literature 1 is a method for bonding fiber-reinforced composite materials composed of a reinforcing fiber and a thermosetting resin to each other by using an adhesive; but, because the thermosetting resin is a matrix resin, welding cannot be used as the method for bonding the fiber-reinforced composite material as it is. Because it takes a time for the adhesive to be cured, there is a problem in that the bonding process is time-consuming. On top of this, the bonding strength thereof was not sufficient.
  • the fiber-reinforced composite material of Patent Literature 3 could be integrated by welding via the thermoplastic resin and exhibited an excellent bonding strength at room temperature, but the bonding strength at high temperature was not sufficient.
  • An object of the present invention is thus to provide: a prepreg giving a laminate suitable as a structural material, the prepreg having an excellent compression strength and an excellent dimensional accuracy of a molded member, being capable of bonding members of the same or different types by welding, expressing an excellent bonding strength, and having an excellent interlaminar fracture toughness value; and a laminate and an integrated product thereof.
  • a prepreg according to the present invention includes the following compositions. That is, a prepreg includes [A], [B], and [C] described below.
  • the [B] further comprises [B']; a ratio of a mole number of an active hydrogen contained in [B'] to a mole number of an epoxy group in an epoxy resin contained in [B] is in a range of 0.6 to 1.1 both inclusive; [C] is present on a surface of the prepreg; and [A] that crosses over a boundary surface between a resin region containing [B] and a resin region containing [C] and that is in contact with both resin regions is present:
  • the laminate according to the present invention includes the following compositions. That is, the laminate includes the composition in which the cured product of the above-described prepreg constitutes at least some of the layers, or includes the following composition. That is, the laminate includes layers containing composition elements [A], [C], and [D] described below,
  • the laminate according to the present invention is a fiber-reinforced resin that can be typically prepared by using a preform containing the prepreg of the present invention.
  • the prepreg and the laminate according to the present invention use a thermosetting resin and a thermoplastic resin, in which not only these two are firmly bonded, but also they can well weld with the same type or a different type of member. Accordingly, the time required for the bonding process can be shortened as compared with a conventional fiber-reinforced composite material using a thermosetting resin and a reinforcing fiber; thus, it is possible to speed up the molding process of a structural member.
  • the laminate can be obtained that exhibits excellent compression strength and bonding strength and is excellent in the dimensional accuracy of the obtained member, as the structural material having excellent properties.
  • the reinforcing fiber of the composition element [A] used in the present invention includes a glass fiber, a carbon fiber, a metal fiber, an aromatic polyamide fiber, a polyaramide fiber, an alumina fiber, a silicon carbide fiber, a boron fiber, a basalt fiber, and the like. These may be used singly or in a combination of two or more of them as appropriate. These reinforcing fibers may be surface treated.
  • the surface treatment includes a metal deposition treatment, a treatment with a coupling agent, a treatment with a sizing agent, and an adhesion treatment with an additive, and the like.
  • the reinforcing fiber shall include those in the state after having been subjected to the treatments as described above.
  • These reinforcing fibers include the reinforcing fiber having an electric conductivity.
  • the carbon fiber is preferably used as the reinforcing fiber because of its low specific gravity, high strength, and high elastic modulus.
  • Illustrative examples of the commercially available product of the carbon fiber include TORAYCA (registered trademark) T800G-24K, TORAYCA (registered trademark) T800S-24K, TORAYCA (registered trademark) T700G-24K, TORAYCA (registered trademark) T700S-24K, TORAYCA (registered trademark) T300-3K, and TORAYCA (registered trademark) T1100G-24K (all are manufactured by Toray Industries, Inc.).
  • the form and arrangement of the reinforcing fiber can be selected as appropriate from the reinforcing fibers arranged in one direction, a laminate of the reinforcing fibers arranged in one direction, a woven fabric, and the like.
  • the reinforcing fibers be long fibers arranged in one direction (fiber bundle) or in the form of continuous fibers such as a woven fabric.
  • the reinforcing fiber bundle may be composed of a plurality of fibers in the same form or a plurality of fibers in different forms.
  • the number of the reinforcing fibers that constitute one reinforcing fiber bundle is usually in the range of 300 to 60,000; but considering the manufacturing of the base material, the number is preferably in the range of 300 to 48,000, while more preferably from 1,000 to 24,000.
  • the range may be a combination of any of the upper limits and any of the lower limits described above.
  • a strand tensile strength thereof measured in accordance with the resin-impregnated strand test method of JIS R7608 (2007), is preferably 5.5 GPa or greater, because the laminate having, in addition to a tensile strength, an excellent bonding strength can be obtained.
  • the strand tensile strength is more preferably 5.8 GPa.
  • the bonding strength here refers to the tensile shear adhesion strength obtained in accordance with ISO 4587:1995 (JIS K6850 (1994)).
  • the reinforcing fiber of the composition element [A] has a surface free energy of preferably in the range of 10 to 50 mJ/m 2 as measured by the Wilhelmy method. By controlling the surface free energy within this range, the reinforcing fiber expresses a high affinity with the epoxy resin composition of [B] or with the epoxy resin cured product of [D] and the thermoplastic resin of [C], and a high bonding strength at the boundary surface in which the reinforcing fiber straddle between a resin region containing [B] or [D] and a resin region containing [C].
  • the surface free energy of the reinforcing fiber is preferably in the range of 15 to 40 mJ/m 2 , while more preferably in the range of 18 to 35 mJ/m 2 .
  • the method to control the surface free energy of the reinforcing fiber includes the method in which an amount of an oxygen-containing functional group such as a carboxyl group and a hydroxyl group is controlled by oxidizing the surface thereof, or the method in which a single compound or a plurality of compounds is attached to the surface thereof. When a plurality of compounds is attached to the surface, a mixture of compounds having a high surface free energy and a low surface free energy may be attached.
  • the method to calculate the surface free energy of the reinforcing fiber will be explained.
  • the surface free energy can be calculated by measuring the contact angle between the reinforcing fiber and each of three solvents (purified water, ethyleneglycol, and tricresyl phosphate) followed by the Owens' approximation method. The procedure is described below, but the measurement equipment and the detailed method thereof are not necessarily limited to the following.
  • DCAT11 manufactured by DataPhysics
  • this is cut into eight fibers having the length of 12 ⁇ 2 mm, and then these are attached in parallel to a specialized holder FH12 (a flat plate whose surface is coated with an adhesive substance) with the distance of 2 to 3 mm between the monofilaments.
  • the tips of the monofilaments are then trimmed and set in DCAT11 of the holder.
  • a cell containing each solvent is brought close to the lower tips of the eight monofilaments at the speed of 0.2 mm/s and immersed to 5 mm from the tip of the monofilaments.
  • the monofilaments are pulled up at the speed of 0.2 mm/s. This operation is repeated four or more times.
  • the force F received by the monofilament while being immersed in the liquid is measured using an electronic balance. This value is used to calculate the contact angle ⁇ by the following equation.
  • COS ⁇ (force F (mN) received by 8 monofilaments)/(8 (number of monofilaments) ⁇ circumference of monofilament (m) ⁇ surface tension of solvent (mJ/m 2 ))
  • the measurement was carried out with regard to the monofilaments extracted from three different locations of the reinforcing fiber bundle. That is, the average contact angle for a total of 24 monofilaments in one reinforcing fiber bundle was calculated.
  • the surface free energy of the reinforcing fiber ⁇ f is calculated as the sum of the surface free energy of the polar component ⁇ p f and the surface free energy of the nonpolar component ⁇ d f .
  • the surface free energy of the polar component ⁇ p f can be calculated as follows: by substituting the components of the surface tension and the contact angle of each liquid into the Owens' approximation formula (which is composed of the polar and the non-polar components of the surface tension specific to each solvent and the contact angle ⁇ ) and plotting them on X and Y, and then, by using the least square method to approximate a straight line, the value is obtained from the square of the slope a.
  • the surface free energy of the nonpolar component ⁇ d f can be obtained by the square of the intercept b.
  • the surface free energy of the reinforcing fiber ⁇ f is the sum of the square of the slope a and the square of the intercept b.
  • Non-polar component of the surface free energy of reinforcing fiber ⁇ d f b 2
  • Total surface free energy ⁇ f a 2 + b 2
  • epoxy resin composition as the composition element [B] in this specification shall mean the resin composition containing more than 50% by mass of an epoxy resin and exhibiting behavior as a thermosetting resin as a whole
  • the average epoxy value of all the epoxy resins included therein is calculated, for example, in the case that this includes two components of epoxy resin 1 and epoxy resin 2, as follows.
  • Average epoxy value meq ./g parts by mass of epoxy resin 1/epoxy equivalent of epoxy resin 1 + parts by mass of epoxy resin 2/epoxy equivalent of epoxy resin 2 / parts by mass of epoxy resin 1 + parts by mass of epoxy resin 2 ⁇ 1000
  • the epoxy equivalent is the value obtained by the method described in JIS K7236 (2009).
  • the average epoxy value of all the included epoxy resins is in the range of 6.0 to 11.0 meq./g both inclusive, the amount of the heat generated at the time of molding can be suppressed; thus, the variation in the degree of curing can be reduced. Accordingly, not only the laminate having an excellent degree of flatness can be obtained, but also the laminate expresses an excellent compression strength, so that this embodiment is preferable. It is more preferable that the average epoxy value of all the included epoxy resins be in the range of 7.5 to 9.0 meq./g both inclusive. This range may be a combination of any of the upper limits and any of the lower limits described above.
  • the active hydrogen equivalent refers to the active hydrogen equivalent that is calculated by identifying the chemical structure and its ratio by means of a liquid chromatography mass spectrometry (LC/MS).
  • LC/MS liquid chromatography mass spectrometry
  • the mole number of the epoxy group in the epoxy resin included in the composition element [B] is calculated as follows.
  • composition element [B] contains epoxy resin of two or more components
  • this is the sum of the mole numbers of the epoxy group in each component.
  • the composition element [B'] contains two or more amine compounds
  • this is the sum of the mole numbers of the active hydrogen in each component and is calculated in the same way as the mole number of the epoxy group.
  • the ratio of the mole number of the active hydrogen in [B'] to the mole number of the epoxy group in [B] is in the range of 0.6 to 1.1 both inclusive
  • the laminate expresses an excellent compressive strength.
  • the heat generated at the time of curing is suppressed and the variation in the degree of curing of the epoxy resin cured product is reduced; thus, the laminate has an excellent degree of flatness.
  • the remaining epoxy group interacts with the thermoplastic resin of a composition element [C], so that the resulting integrated product expresses an excellent bonding strength.
  • the ratio of the mole number of the active hydrogen contained in [B'] to the mole number of the epoxy group contained in [B] be in the range of 0.65 to 0.95 both inclusive. This range may be a combination of any of the upper limits and any of the lower limits described above.
  • the epoxy resin cured product of a composition element [D] in the laminate according to the present invention is typically a thermally cured product of the epoxy resin composition of the composition element [B] containing the amine compound of the composition element [B'] in the prepreg according to the present invention.
  • the temperature condition for the thermal curing may be set appropriately in accordance with the epoxy resin, the amine compound, and the curing accelerator including the kinds and amounts thereof. For example, when diaminodiphenylsulfone is used as the amine compound, the temperature condition of 180°C for 2 hours may be preferably used, and when dicyandiamide is used as the amine compound, the temperature condition of 135°C for 2 hours may be preferably used.
  • epoxy resin to be used in the composition element [B] include bisphenol epoxy resins such as a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol AD epoxy resin, a bisphenol S epoxy resin, and a brominated epoxy resin such as a tetrabromobisphenol A diglycidyl ether, an epoxy resin having a biphenyl skeleton, an epoxy resin having a naphthalene skeleton, an epoxy resin having a dicyclopentadiene skeleton, novolac epoxy resins such as a phenol novolac epoxy resin and a cresol novolac epoxy resin, N,N,O-triglycidyl-m-aminophenol, N,N,O-triglycidyl-p-aminophenol, N,N,O-triglycidyl-4-amino-3-methylphenol, N,N,N',N'-tetraglycidyl-4,4'-methylenedianiline,
  • bisphenol epoxy resins
  • the cured product having a high heat resistance can be obtained; so, this embodiment is more preferable.
  • the content thereof is still more preferably in the range of 80 to 100 parts by mass.
  • Illustrative examples of the glycidylamine epoxy resin containing 3 or more glycidyl groups include N,N,O-triglycidyl-m-aminophenol, N,N,O-triglycidyl-p-aminophenol, N,N,O-triglycidyl-4-amino-3-methylphenol, N,N,N',N'-tetraglycidyl-4,4'-methylenedianiline, N,N,N',N'-tetraglycidyl-2,2'-diethyl-4,4'-methylenedianiline, and N,N,N',N'-tetraglycidyl-m-xylylenediamine.
  • Illustrative examples of the amine compound to be used in the composition element [B'] include a dicyandiamide, an aromatic amine compound, a tetramethylguanidine, and a thiourea-added amine.
  • the epoxy resin having an excellent heat resistance can be obtained.
  • the aromatic amine compound include 3,3'-diisopropyl-4,4'-diaminodiphenylsulfone, 3,3'-di-t-butyl-4,4'-diaminodiphenylsulfone, 3,3'-diethyl-5,5'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-di-t-butyl-5,5'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylsulfone, 3,3'-
  • the epoxy resin composition of the composition element [B] according to the present invention in which the amine compound of [B'] is the main component as the curing agent, may contain another curing agent or curing accelerator. It is preferable that the mass of [B'] relative to the total mass of the curing agent and the curing accelerator contained in the epoxy resin composition of [B] be 80% or more.
  • the other curing agent include an acid anhydride and a phenol novolac compound.
  • Illustrative examples of the curing accelerator include phosphorus-based curing accelerators such as triphenylphosphine and a tetraarylphosphonium tetraarylborate, as well as a cationic polymerization initiator, a tertiary amine, an imidazole compound, and a urea compound.
  • phosphorus-based curing accelerators such as triphenylphosphine and a tetraarylphosphonium tetraarylborate, as well as a cationic polymerization initiator, a tertiary amine, an imidazole compound, and a urea compound.
  • the epoxy resin composition of the composition element [B] contain, as a viscosity controller, a thermoplastic resin component that is soluble in the epoxy resin in the state of being dissolved therein.
  • the thermoplastic resin component described above is a thermoplastic resin component other than a thermoplastic resin included in the composition element [C].
  • soluble in the epoxy resin means that there is a temperature range in which the epoxy resin component being mixed with the thermosetting resin forms a homogeneous phase upon heating or heating with stirring.
  • the term “forming a homogeneous phase” means that there is no separation by a visual observation.
  • state of being dissolved refers to the state in which the epoxy resin including the thermoplastic resin component is in a homogeneous phase in a certain temperature range. Once a homogeneous phase is formed in a certain temperature range, it does not matter whether or not separation occurs outside this temperature range, for example, at room temperature.
  • the epoxy resin component that is soluble in the thermosetting resin of the composition element [B] is preferably the thermoplastic resin generally having in the main chain thereof a bond selected from the group consisting of a carbon-carbon bond, an amide bond, an imide bond, an ester bond, an ether bond, a carbonate bond, a urethane bond, a thioether bond, a sulfone bond, and a carbonyl bond.
  • the thermoplastic resin component may partially have a cross-linked structure; and also, this may be crystalline or amorphous.
  • preferable is at least one resin selected from the group consisting of polyamide, polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide, polyarylate, polyester, polyamideimide, polyimide, polyetherimide, polyimide having a phenyl trimethylindane structure, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyaramide, polyvinyl formal, polyvinyl butyral, a phenoxy resin, polyether nitrile and polybenzimidazole.
  • resin selected from the group consisting of polyamide, polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide, polyarylate, polyester, polyamideimide, polyimide, polyetherimide, polyimide having a phenyl trimethylindane structure, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyaramide, polyviny
  • the glass transition temperature thereof is preferably 150°C or higher, while more preferably 170°C or higher; so, polyetherimide and polyethersulfone are mentioned as preferable examples for this.
  • thermoplastic resin composition element [C] thermoplastic resin compostion
  • thermoplastic resin compostion as the composition element [C] herein means a resin composition that contains more than 50% by mass of the thermoplastic resin and exhibits the behavior of the thermoplastic resin as a whole); then, illustrative examples thereof include: polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and a liquid crystal polyester; polyolefins such as polyethylene, polypropylene, and polybutylene; a styrene resin, a urethane resin, and polyoxymethylene; polyamides such as polyamide 6 and polyamide 66; polycarbonate, polymethyl methacrylate, polyvinyl chloride, polyphenylene sulfide, polyphenylene ether, a modified polyphenylene ether, polyimide, polyamideimide, polyetherimide, polysulfone, a
  • the thermoplastic resin may also be a copolymer or a modified version of the above-mentioned resins and/or a blend of two or more of them.
  • the composition element [C] includes preferably one or two or more resins selected from polyarylene ether ketone, polyphenylene sulfide, and polyetherimide with the amount thereof being 60% or more by mass therein.
  • An elastomer or a rubber component may be added to improve the impact resistance.
  • other fillers and additives may be included as appropriate in accordance with the use and the like so far as such addition does not impair the purpose of the present invention.
  • Illustrative examples thereof include an inorganic filler, a flame retardant, a conductive agent, a crystal nucleating agent, a UV absorber, an antioxidant, a vibration-damping agent, an antibacterial agent, an insect repellent, an odor repellent, an anti-coloring agent, a heat stabilizer, a mold release agent, an antistatic agent, a plasticizer, a lubricant, a colorant, a pigment, a dye, a foaming agent, an antifoaming agent, and a coupling agent.
  • thermoplastic resin contained in the composition element [C] has a functional group exhibiting a reactivity with the epoxy group present at the terminal or in the main skeleton, a covalent bond is formed by chemical reaction with the remaining epoxy group thereby giving an integrated product having an excellent bonding strength; thus, this is a preferable embodiment.
  • the functional group exhibiting a reactivity with the epoxy group include a carboxyl group, an amino group, a hydroxyl group, and an isocyanate group.
  • the prepreg according to the present invention there is a reinforcing fiber of [A] that straddles the boundary surface between the resin region containing [B] and the resin region containing [C] and is in contact with both the resin regions.
  • [A] chemically and/or physically bonds with [B] and [C]; thus, this causes exfoliation of the resin region containing [B] from the resin region containing [C] to be difficult, thereby expressing an excellent bonding strength.
  • the chemical and/or physical bonding of the composition element [A] on the boundary surface with the composition element [B] and the composition element [C] improves the adhesion of the resin region containing the composition element [B] to the resin region containing the composition element [C].
  • FIG. 1 is a schematic diagram of the prepreg or the laminate according to the present invention
  • FIG. 2 is a schematic diagram of a cross section that is perpendicular to the prepreg plane or the laminate plane, described in FIG. 1 as a cross section observation surface 5, and is for the sake of explanation about the method to measure the roughness average length RSm and the roughness average height Rc.
  • layered and adjacent means the state in which, for example, as illustrated in FIG. 2 , a resin region 7 containing [C] and a resin region 8 containing [B], which are continuous in the plane direction, exist in close contact with each other while forming a boundary surface 10 in the cross section obtained by cutting perpendicularly to the prepreg plane direction.
  • the resin region 7 containing [C] is not in a layered and continuous state, but exists in a particulate, a fibrous, an unwoven, or other form, the ratio of the area where the epoxy resin included in [B] is exposed on the surface increases and the covering rate of [C] on the outermost surface decreases, so that the welding property tends to be lowered.
  • a roughness average length RSm of 100 ⁇ m or less and a roughness average height Rc of 3.5 ⁇ m or more are preferable in order to improve the bonding strength, where these length and height are of a cross section curve formed by the boundary of the two resins and are defined by JIS B0601 (2001).
  • the roughness average length RSm is 100 ⁇ m or less, not only the chemical and/or physical bonding force but also the mechanical bonding force of interlocking makes it difficult for the resin region containing the composition element [B] and the resin region containing the composition element [C] to be exfoliated from each other.
  • the lower limit thereof is not particularly restricted; but from the viewpoint of avoiding a decrease in the mechanical bonding strength due to stress concentration, this is preferably 15 ⁇ m or more.
  • the roughness average height Rc of the cross section curve is 3.5 ⁇ m or higher, not only the mechanical bonding force due to interlocking is expressed, but also the composition element [A] on the boundary surface chemically and/or physically bonds with the composition element [B] and the composition element [C], so that the adhesion of the resin region containing the composition element [B] with the resin region containing the composition element [C] is improved.
  • the preferable range of the roughness average height Rc of the cross sectional curve is 10 ⁇ m or more; with this, the composition element [A] is more easily included in both the resin regions, thereby enhancing the adhesion furthermore. This is especially preferable when this is 20 ⁇ m or more.
  • the upper limit thereof is not particularly restricted; but from the viewpoint of avoiding a decrease in the mechanical bonding strength due to stress concentration, this is preferably 100 ⁇ m or less.
  • the measurement of the roughness average height Rc and the roughness average length RSm of the cross section curve known methods may be used. For example, after the composition element [B] is cured, the measurement may be made from the cross section image obtained by using an X-ray CT, from the elemental analysis mapping image obtained by using an energy dispersive X-ray spectrometer (EDS), or from the cross section observation image obtained by using an optical microscope, a scanning electron microscope (SEM), or a transmission electron microscope (TEM). In these observations, the composition element [B] and/or the composition element [C] may be stained to adjust the contrast. In the image obtained by any of the above methods, the roughness average height Rc and the roughness average length RSm of the cross section curve are measured in the area of a 500 ⁇ m square.
  • EDS energy dispersive X-ray spectrometer
  • TEM transmission electron microscope
  • FIG. 2 An example of the method for measuring the roughness average height Rc and the roughness average length RSm of the cross section curve is illustrated in FIG. 2 .
  • the resin region 7 containing the composition element [C] is in close contact with the resin region 8 containing the composition element [B]; and this is illustrated as the boundary surface 10 in the observed image 9.
  • a plurality of the composition elements [A] 6 is present on the boundary surface 10.
  • the basis weight of the thermoplastic resin of the composition element [C] be 10 g/m 2 or more.
  • the basis weight of 10 g/m 2 or more is preferable, because this provides a sufficient thickness to express an excellent bonding strength.
  • the basis weight of 20 g/m 2 is more preferable.
  • the upper limit thereof is not particularly restricted, this is preferably 500 g/m 2 or less, because this amount of the thermoplastic resin is not too much relative to the reinforcing fiber, so that the laminate having excellent specific strength and specific modulus can be obtained.
  • the basis weight refers to the mass (g) of the composition element [C] included in 1 m 2 of the prepreg.
  • the amount of the reinforcing fiber per unit area is preferably in the range of 30 to 2,000 g/m 2 .
  • the amount of the reinforcing fiber is 30 g/m 2 or more, the number of the laminate films to obtain a predetermined thickness can be reduced in the laminate molding, so that the workability is likely to be improved.
  • the amount of the reinforcing fiber is 2,000 g/m 2 or less, the draping property of the prepreg is likely to be improved.
  • the content of the reinforcing fiber in the prepreg according to the present invention is preferably in the range of 30 to 90% by mass, more preferably in the range of 35 to 85% by mass, while still more preferably in the range of 40 to 80% by mass.
  • the range may be a combination of any of the upper limits and any of the lower limits described above.
  • the content of the reinforcing fiber is 30% or more by mass, the amount of resin is not too much relative to the fiber; thus, the laminate's advantages of the excellent specific strength and of the specific modulus is likely to be obtained, and upon molding of the laminate, the amount of heat generated at the time of curing is unlikely to become excessively high.
  • the content of the reinforcing fiber is 90% or less by mass, the chance of poor impregnation of the resin is likely to be reduced thereby leading to the decrease in formation of the void in the resulting laminate.
  • Another aspect of the present invention is the laminate that is produced by the method in which the preform having at least some of the layers thereof composed of the prepreg according to present invention is cured by pressurizing and heating, namely, the laminate having at least some of the layers thereof composed of the cured product of the prepreg according to the present invention; the preform being produced by laminating a plurality of the prepregs according to the present invention, or by laminating the prepreg according to the present invention with a prepreg other than the prepreg according to the present invention.
  • the method for heating and pressurizing include a press molding method, an autoclave molding method, a bag molding method, a wrapping tape method, and an internal pressure molding method.
  • Still another aspect of the present invention is a laminate including layers containing composition elements [A], [C], and [D], in which a reinforcing fiber of [A] that straddles a boundary surface between a resin region containing [C] and a resin region containing [D] and is in contact with both the resin regions is present.
  • the prepreg When the prepreg is viewed in a plane, from a direction that differs by an angle of 45 degrees, regardless of whether clockwise or counterclockwise, to a fiber direction of any [A] in contact with both the resin regions, a cross section perpendicular to the plane of the laminate containing [A] that straddles both the resin regions is obtained; in this cross section, namely, in the cross section that is obtained by cutting or the like perpendicularly to the plane direction of the laminate, the roughness average length RSm of 100 ⁇ m or less and the roughness average height Rc of 3.5 ⁇ m or more are preferable.
  • the length and height are of a cross section curve formed by a boundary surface of the two adhered resin regions and defined by JIS B0601 (2001).
  • the roughness average height Rc is more preferably 10 ⁇ m or more.
  • the lower limit of RSm and the upper limit of Rc are not particularly restricted; but from the concern of a decrease in the mechanical bonding strength due to stress concentration, it is preferable that RSm be 15 ⁇ m or more and Rc be 100 ⁇ m or less.
  • the roughness average height Rc and roughness average length RSm of the cross section curve may be obtained by the method similar to the measurement method used in the prepreg according to the present invention as described before.
  • Illustrative examples of the molding method of the laminate according to the present invention include a press molding method, an autoclave molding method, a bag molding method, a wrapping tape method, an internal pressure molding method, a hand layup method, a filament winding method, a pultrusion method, a resin injection molding method, and a resin transfer molding method.
  • the thermoplastic resin composition of the composition element [C] be present on the surface thereof.
  • the layer containing [A], [C] and [D] be present as the outermost layer, and that [C] be exposed to the surface thereof.
  • the composition element [C] be present both on the surface of and inside the laminate; namely, it is preferable to have the layer containing [A], [C], and [D] also as an inner layer.
  • the laminate according to the present invention can weld the same or different members via the composition element [C]; on the other hand, when the thermoplastic resin of the composition element [C] is present also inside the laminate, an excellent interlaminar fracture toughness value (G IIC ) is obtained.
  • the integrated product having integrated (welded) with the laminate via the composition element [C] can be obtained.
  • the different type of member include a member made of a thermoplastic resin and a member made of a metallic material.
  • the member made of the thermoplastic resin may contain a reinforcing fiber, a filler, and the like.
  • the integration method there is no particular restriction on the integration method; here, illustrative examples thereof include a thermal welding, a vibration welding, an ultrasonic welding, a laser welding, a resistance welding, an induction welding, an insert injection molding, and an outsert injection molding.
  • the strength of the bonding portion of the integrated product can be evaluated in accordance with ISO 4587:1995 (JIS K6850 (1994)).
  • the tensile shear adhesion strength measured in accordance with ISO 4587:1995 is preferably 25 MPa or more, while more preferably 28 MPa or more.
  • the laminate can be used for bonding of a structural material with the tensile shear adhesion strength of 20 MPa or greater, and the tensile shear adhesion strength here is higher than the tensile shear adhesion strength of a common adhesive measured under the testing ambient temperature of 23°C (about 10 MPa).
  • the laminate according to the present invention is preferably used for an aircraft structural member, a wind turbine blade, an automotive exterior plate, computer applications such as an IC tray and a housing of a laptop computer, sporting goods such as a golf club shaft and a tennis racket, etc.
  • the unit "part" in the composition ratio means part by mass unless otherwise specifically noted.
  • the measurement of various characteristics was performed under an ambient temperature of 23°C and the relative humidity of 50% unless otherwise specifically noted.
  • composition elements [A], [B], [B'], and [C] described below were used.
  • the composition elements used in each Example and Comparative Example are listed in Tables 1 to 3.
  • the compounds used as the sizing agent for the carbon fiber as well as the surface free energies after application of the sizing agent are as follows.
  • the melting point of the thermoplastic resin was measured using a differential scanning calorimeter (DSC) in accordance with JIS K7121 (2012). In the case when a plurality of melting points was observed, such as in the case of a mixture, the highest melting point was used as the melting point of the thermoplastic resin.
  • DSC differential scanning calorimeter
  • Epoxy resin compositions for each of the specific examples listed in Table 1 were prepared using the following compounds.
  • the epoxy resin composition prepared by the above method was charged into a molding machine; then, the temperature was raised from 30°C to 180°C with the rate of 1.5°C/min in a hot air dryer. After thermally cured at 180°C for 120 minutes, the temperature was lowered to 30°C with the rate of 2.5°C/min to obtain a plate-like resin cured product having the thickness of 2 mm. From the epoxy resin cured product thus obtained, the specific examples listed in Table 1 were evaluated using the methods described below.
  • a test specimen having the thickness of 12.7 mm and the length of 45 mm was cut out; then, the test specimen was dried at 60°C in a vacuum oven for 24 hours.
  • the storage modulus curve thereof was obtained by a dynamic viscoelasticity testing according to JIS K 7244-7 (2007); then, the value of the temperature at the intersection of the tangent line in the glass state and the tangent line in the transition state in the storage modulus curve was defined as the glass transition temperature.
  • a test specimen having the length of 60 mm and the thickness of 10 mm was cut out, and then, this was dried in a vacuum oven at 60°C for 24 hours. Next, this was subjected to a three-point bending test at a testing speed of 2.5 mm/min and a distance of 32 mm between the fulcrum points using a universal testing machine ("Instron” (registered trademark) 5565 model P8564, manufactured by Instron Japan) to obtain the flexural modulus in accordance with JIS K7171 (1994).
  • Instron registered trademark
  • Prepregs were prepared by the following two methods. The composition elements used in Examples are described in Tables 2 and Table 3.
  • Prepregs [I] and [II] prepared as described above were cut into predetermined size to obtain two sheets of prepreg [I] and six sheets of prepreg [II].
  • the preforms were prepared by stacking them to [0°/90°] 2s (the symbol s indicates a mirror symmetry), in which the axial direction of the reinforcing fiber is defined as 0° and the orthogonal direction to the axis is defined as 90°.
  • the two outermost layers of both sides were laminated with prepreg [I], and both surface layers of the preform were formed so as to be the thermoplastic resin layers containing the composition element [C].
  • the preform was set in the press mold, and then pressurized and heated by using a press machine with the pressure of 0.6 MPa at 180°C for 120 minutes with keeping the shape of the preform by using a jig or a spacer, if necessary, to obtain the laminate.
  • the resulting laminate was cut into two pieces having the width of 250 mm and the length of 92.5 mm with the 0° direction as the longitudinal direction of the specimen; then, they were dried in a vacuum oven for 24 hours.
  • two panels were overlapped with the width of 25 mm ⁇ the length of 12.5 mm and the 0° direction as the longitudinal direction; then, this was kept under the pressure of 3 MPa at the temperature above the melting point of the used thermoplastic resin of the composition element [C] by 20°C for 1 minute thereby welding the overlapped surfaces to obtain the integrally molded product.
  • the resulting integrated product was adhered with a tab in accordance with ISO 4587:1995 (JIS K6850 (1994)); then, this was cut at the width of 25 mm to obtain the specimen.
  • the specimen thereby obtained was dried in a vacuum oven for 24 hours, and then the tensile shear adhesion strength thereof was measured at an ambient temperature of 23°C in accordance with ISO 4587:1995 (JIS K6850 (1994)). The evaluation was made as follows on the basis of the measurement results. The results are described in Tables.
  • Prepregs [I] and [II] prepared as described above were cut into predetermined size to obtain two sheets of prepreg [I] and four sheets of prepreg [II]. Two sheets of the prepreg [I] were placed as the outermost layers on both sides and the prepregs (II) were interposed between them; thus, the total 6 sheets of the prepregs were stacked in such a way as to be all in the same direction as the reinforcing fiber direction to obtain a preform. At this time, the preform was arranged such that both surface layers were the thermoplastic resin layers containing the composition element [C].
  • the preform was set in the press mold, and then pressurized and heated by using a press machine with the pressure of 0.6 MPa at 180°C for 120 minutes with keeping the shape of the preform by using a jig or a spacer, if necessary, to obtain the laminate.
  • Prepregs [I] and [II] prepared as described above were cut into the size of 250 mm long and 125 mm wide to obtain two prepregs [I] and six prepregs [II].
  • Two sheets of the prepreg [I] were placed as the outermost layers on both sides and the prepregs (II) were interposed between them; thus, the total 8 sheets of the prepregs were stacked in such a way as to be all in the same direction as the reinforcing fiber direction to obtain a preform.
  • the preform was arranged such that both surface layers were the thermoplastic resin layers containing the composition element [C].
  • the preform was set in the press mold, and then pressurized and heated by using a press machine with the pressure of 0.6 MPa at 180°C for 120 minutes with keeping the shape of the preform by using a jig or a spacer, if necessary, to obtain the laminate.
  • the degree of flatness of the resulting laminate was evaluated in accordance with JIS B7513 (1992).
  • the resulting laminate was cut to the size having the length of 250 mm and the width of 125 mm; then, three of the four edge points of the laminate were grounded on a precision surface plate, and the height of the remaining one point from the plate was obtained.
  • the height of each of the four edge points of the laminate from the plate thereof was obtained by the above method, in which the point not grounded on the precision surface plate was made the one point as described above. This measurement was repeated in turn for all points; then, the highest value of the four heights from the surface plate was defined as the degree of flatness of the laminate. From the measurement results, the evaluation was made as follows. The results are described in Tables.
  • the prepreg [I] prepared above was cut to a predetermined size, and a total of 20 sheets thereof were stacked in such a way as to be in the same direction as the reinforcing fiber direction. Then, the preform was prepared by inserting a release film for pre-crack introduction at the position between the 10th and 11th sheets in the middle. The preform was set in the press mold, and then pressurized and heated by using a press machine with the pressure of 0.6 MPa at 180°C for 120 minutes with keeping the shape of the preform by using a jig or a spacer, if necessary, to obtain the laminate.
  • the laminate described in (1) Measurement Method of Tensile Shear Adhesion Strength was used; then, the image was taken using an optical microscope with the magnification of 1000 times in the observing cross section obtained by cutting perpendicularly to the plane direction, and the rest of the measurement was performed in the same manner as the case of the prepreg described above.
  • Comparative Example 3 a polyamide 6 film ("Amilan” (registered trademark) CM1007 (manufactured by Toray Industries, Inc.)) with the basis weight of 50 g/m 2 was attached to both surfaces of the reinforcing fiber sheet arranged in plane to one direction; then, this was pressurized with heating at 250°C to obtain the prepreg of a reinforcing carbon fiber with the basis weight of 193 g/m 2 . The obtained prepreg was cut to a predetermined size; then, 8 sheets thereof were stacked to [0°/90°] 2s or to the same direction, or 6 sheets to the same direction for evaluations of the bonding strength, of the degree of flatness, and of the compression strength.
  • Similar registered trademark
  • CM1007 manufactured by Toray Industries, Inc.
  • Example 20 the prepreg [I] was cut to a predetermined size, and a total of 20 sheets thereof were stacked in such a way as to be in the same direction as the reinforcing fiber direction; and a release film for pre-crack introduction was inserted at the position between the 10th and 11th sheets in the middle to obtain a preform.
  • Comparative Example 5 polyamide particles (SP-500, manufactured by Toray Industries, Inc.) were evenly spread on one surface of the prepreg [II] (not containing composition element [C]) having been cut to a predetermined size such that the amount of the particles per unit area of prepreg might become 7 g/m 2 . Then, in the same way as Example 20, after lamination, a release film was inserted to obtain a preform.
  • SP-500 manufactured by Toray Industries, Inc.
  • Example 20 and Comparative Examples 4 and 5 the obtained preform was pressurized by a press machine with a pressure of 0.6 MPa with heating at 180°C for 120 minutes to obtain the laminate; then, with the method described in Examples, the interlaminar fracture toughness value (G IIC ) thereof was evaluated.
  • Epoxy resin composition Composition element [B] Epoxy resin Bisphenol A epoxy ("jER (registered trademark)" 825) 80 40 20 20 20 20 20 80 80 80 20 Tetraglycidyl diaminodiphenyl methane ("Araldite (registered trademark)" MY721) 20 60 80 80 80 80 80 20 20 80 Aminophenol epoxy ("Araldite (registered trademark)" MY0500) 100 Bisphenol A epoxy ("jER (registered trademark)" 1001) 20 Composition element [B'] Curing agent containing amine compound 4,4'-Diaminodiphenyl sulfone (Seika Cure S) 28 33 36 32 46 51 57 56 28 47 26 Diethyltoluenediamine (“Aradur (registered trademark)" 5200) 20 Viscosity controller Polyether sulfone ( "SUMIKAEXCEL (registered trademark)" PES500
  • Example 12 Example 13 Composition element [A] Reinforcing fiber CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 CF1 Epoxy resin composition B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 B-10 B-3 B-3 B-3 Composition element [C] Thermoplastic resin PA6 PA6 PA6 PA6 PA6 PA6 PA6 PA6 PA6 PA6 PA6 PA6 PA6 PA6 PA6 PA6 PPS PEKK1 PEKK2 Epoxy resin composition data Average epoxy value 6.4 7.6 8.3 8.3 8.3 8.3 8.3 10.0 5.0 6.4 8.3 8.3 8.3 8.3 Average amine value 16.1 16.1 16.1 16.1 16.1 16.1 16.1 16.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
EP20897743.9A 2019-12-11 2020-11-20 Préimprégné, stratifié et article moulé intégré Pending EP4074761A4 (fr)

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JP3440615B2 (ja) 1995-03-22 2003-08-25 東レ株式会社 プリプレグおよび繊維強化複合材料
JPH10138354A (ja) 1996-11-08 1998-05-26 Yamaha Corp 炭素繊維強化樹脂成形物とその製造方法
TWI304321B (en) * 2002-12-27 2008-12-11 Toray Industries Layered products, electromagnetic wave shielding molded articles and method for production thereof
CN100421924C (zh) * 2002-12-27 2008-10-01 东丽株式会社 层压品及其制造方法
JP4543696B2 (ja) * 2003-02-21 2010-09-15 東レ株式会社 繊維強化複合材料およびその製造方法並びに一体化成形品
WO2012111743A1 (fr) * 2011-02-16 2012-08-23 三菱レイヨン株式会社 Composition de résine époxy, préimprégné et matériau composite renforcé de fibres
JP2012193322A (ja) * 2011-03-18 2012-10-11 Toray Ind Inc プリプレグ、および炭素繊維強化複合材料
US20140037939A1 (en) * 2011-04-27 2014-02-06 Toray Industries, Inc. Prepreg and fiber reinforced composite material, and process for producing prepreg
JP6102319B2 (ja) * 2012-02-28 2017-03-29 住友ベークライト株式会社 プリプレグおよびプリプレグの製造方法
US9574081B2 (en) * 2012-08-20 2017-02-21 Mitsubishi Rayon Co., Ltd. Epoxy-resin composition, and film, prepreg and fiber-reinforced plastic using the same
JP6497027B2 (ja) * 2014-10-29 2019-04-10 東レ株式会社 エポキシ樹脂組成物、樹脂硬化物、プリプレグおよび繊維強化複合材料
US9821530B2 (en) * 2014-11-25 2017-11-21 The Boeing Company Composite laminate including interlayers with through-plane regions fused to fiber beds
JP7052207B2 (ja) 2017-03-27 2022-04-12 三菱ケミカル株式会社 接着構造部材
JP7183793B2 (ja) * 2017-11-14 2022-12-06 東レ株式会社 プリプレグおよび繊維強化複合材料
EP3786208A4 (fr) * 2018-04-23 2021-06-16 Mitsubishi Chemical Corporation Composition de résine époxy pour matériaux composites renforcés par fibres de carbone, préimprégné et matériau composite renforcé par fibres de carbone

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TW202132438A (zh) 2021-09-01
JPWO2021117460A1 (fr) 2021-06-17
EP4074761A4 (fr) 2024-01-03

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